A comparative study of the electrochemical and proton-reduction behaviour of diphosphine-dithiolate complexes [M2(CO)4(μ-dppm){μ-S(CH2)nS}] (M = Fe, Ru; n = 2, 3)

Shishir Ghosh; Shariff E. Kabir; Graeme Hogarth

doi:10.1007/s11243-017-0164-6

A comparative study of the electrochemical and proton-reduction behaviour of diphosphine-dithiolate complexes [M₂(CO)₄(μ-dppm){μ-S(CH₂)_nS}] (M = Fe, Ru; n = 2, 3)

Shishir Ghosh^*
, Shariff E. Kabir
, Graeme Hogarth

^*Corresponding author for this work

Chemistry

Jahangirnagar University

Research output: Contribution to journal › Article › peer-review

11 Citations (Scopus)

151 Downloads (Pure)

Abstract

The electrochemistry of dppm-bridged dithiolate complexes [M2(CO)4(μ-dppm){μ-S(CH2)nS}] (M = Fe, Ru; n = 2, 3) has been studied by cyclic voltammetry. The diiron complexes show similar electrochemical responses in CH2Cl2 but differ significantly in MeCN, while the diruthenium complexes change only slightly with changes in the dithiolate backbone and solvent. Proton-reduction studies in MeCN with HBF4·Et2O as the proton source show that all are active catalysts for proton reduction in their singly reduced state. An additional catalytic event is observed for all, resulting from their partial protonation giving [M2(CO)4(μ-dppm){μ-S(CH2)nS}(μ-H)][BF4]. The diiron complexes show better long-term stability to acids, the diruthenium complexes degrading at high acid concentrations.

Original language	English
Pages (from-to)	1-7
Number of pages	7
Journal	Transition Metal Chemistry
Early online date	24 Jul 2017
DOIs	https://doi.org/10.1007/s11243-017-0164-6
Publication status	E-pub ahead of print - 24 Jul 2017

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A comparative study_GHOSH_Accepted 6 Jul 17_GOLD VoR_CC-BYFinal published version, 1.37 MBLicence: CC BY

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title = "A comparative study of the electrochemical and proton-reduction behaviour of diphosphine-dithiolate complexes [M2(CO)4(μ-dppm)\{μ-S(CH2)nS\}] (M = Fe, Ru; n = 2, 3)",

abstract = "The electrochemistry of dppm-bridged dithiolate complexes [M2(CO)4(μ-dppm)\{μ-S(CH2)nS\}] (M = Fe, Ru; n = 2, 3) has been studied by cyclic voltammetry. The diiron complexes show similar electrochemical responses in CH2Cl2 but differ significantly in MeCN, while the diruthenium complexes change only slightly with changes in the dithiolate backbone and solvent. Proton-reduction studies in MeCN with HBF4·Et2O as the proton source show that all are active catalysts for proton reduction in their singly reduced state. An additional catalytic event is observed for all, resulting from their partial protonation giving [M2(CO)4(μ-dppm)\{μ-S(CH2)nS\}(μ-H)][BF4]. The diiron complexes show better long-term stability to acids, the diruthenium complexes degrading at high acid concentrations.",

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AU - Ghosh, Shishir

AU - Kabir, Shariff E.

AU - Hogarth, Graeme

PY - 2017/7/24

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N2 - The electrochemistry of dppm-bridged dithiolate complexes [M2(CO)4(μ-dppm){μ-S(CH2)nS}] (M = Fe, Ru; n = 2, 3) has been studied by cyclic voltammetry. The diiron complexes show similar electrochemical responses in CH2Cl2 but differ significantly in MeCN, while the diruthenium complexes change only slightly with changes in the dithiolate backbone and solvent. Proton-reduction studies in MeCN with HBF4·Et2O as the proton source show that all are active catalysts for proton reduction in their singly reduced state. An additional catalytic event is observed for all, resulting from their partial protonation giving [M2(CO)4(μ-dppm){μ-S(CH2)nS}(μ-H)][BF4]. The diiron complexes show better long-term stability to acids, the diruthenium complexes degrading at high acid concentrations.

AB - The electrochemistry of dppm-bridged dithiolate complexes [M2(CO)4(μ-dppm){μ-S(CH2)nS}] (M = Fe, Ru; n = 2, 3) has been studied by cyclic voltammetry. The diiron complexes show similar electrochemical responses in CH2Cl2 but differ significantly in MeCN, while the diruthenium complexes change only slightly with changes in the dithiolate backbone and solvent. Proton-reduction studies in MeCN with HBF4·Et2O as the proton source show that all are active catalysts for proton reduction in their singly reduced state. An additional catalytic event is observed for all, resulting from their partial protonation giving [M2(CO)4(μ-dppm){μ-S(CH2)nS}(μ-H)][BF4]. The diiron complexes show better long-term stability to acids, the diruthenium complexes degrading at high acid concentrations.

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A comparative study of the electrochemical and proton-reduction behaviour of diphosphine-dithiolate complexes [M₂(CO)₄(μ-dppm){μ-S(CH₂)_nS}] (M = Fe, Ru; n = 2, 3)

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